CN1061320C - Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation - Google Patents
Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation Download PDFInfo
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- CN1061320C CN1061320C CN96115030A CN96115030A CN1061320C CN 1061320 C CN1061320 C CN 1061320C CN 96115030 A CN96115030 A CN 96115030A CN 96115030 A CN96115030 A CN 96115030A CN 1061320 C CN1061320 C CN 1061320C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims description 5
- 238000007254 oxidation reaction Methods 0.000 title claims description 5
- 229910052759 nickel Inorganic materials 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 238000013459 approach Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018505 Ni—Mg Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
Description
本发明为甲烷直接氧化制合成气提供一种廉价的催化剂。该催化剂在大空速条件下(＞105h-1)，具有高活性、高选择性和抗积碳性能好的优点。The invention provides a cheap catalyst for the direct oxidation of methane to synthesis gas. The catalyst has the advantages of high activity, high selectivity and good carbon deposition resistance under the condition of large space velocity (>10 5 h -1 ).
甲烷直接氧化制合成气的反应为：The reaction of direct oxidation of methane to synthesis gas is:
自九十年代初国外开始有报导。该反应具有轻放热、反应产物H2/CO=2.0(适合于后继的甲醇和费一托合成)，并可在高空速条件下操作等优点。因此，很具有替代常规的甲烷水蒸汽重整制合成气的可能性。目前，从文献报导的结果来看，所用的催化剂中一般是负载型的Rh、Pt、Ir和Ru等Ⅷ族金属。其中Rh的活性高，抗积碳性能好。而Ni上易产生积碳，且Ni在操作过程中易流失。有关这方面工作的专利不多，并且专利报导中所用的催化剂活性组份主要集中在贵金属类。如欧洲专利640559用Pt族元素(含量在0.1-20％)；欧洲专利640561主要用Rh/La2Zr2O7。因其主要组份都为贵金属，所以用于工业过程时，催化剂成本昂贵，实用性不大。因此，开发一种新型的可望成为工业生产的催化剂是该技术推广应用的关键。It has been reported abroad since the early 1990s. The reaction has the advantages of light exotherm, reaction product H 2 /CO=2.0 (suitable for subsequent methanol and Fischer-Tropsch synthesis), and can be operated under high space velocity conditions. Therefore, it is very possible to replace the conventional steam reforming of methane to produce synthesis gas. At present, according to the results reported in the literature, the catalysts used are generally supported Group VIII metals such as Rh, Pt, Ir and Ru. Among them, Rh has high activity and good anti-carbon deposition performance. However, carbon deposition is easy to occur on Ni, and Ni is easy to lose during operation. There are not many patents related to the work in this area, and the catalyst active components used in the patent reports are mainly concentrated in noble metals. For example, European Patent 640559 uses Pt group elements (content 0.1-20%); European Patent 640561 mainly uses Rh/La 2 Zr 2 O 7 . Because the main components are noble metals, the catalyst is expensive and not practical when used in industrial processes. Therefore, the development of a new type of catalyst that is expected to be industrially produced is the key to the popularization and application of this technology.
本发明的目的是在非贵金属Ni基催化剂上通过添加助剂的调变作用制备出一种活性高，稳定性好，抗积碳能力强的催化剂。用于大空速条件下直接氧化甲烷制合成气，其活性接近相同条件下的贵金属催化剂。The purpose of the invention is to prepare a catalyst with high activity, good stability and strong anti-coking ability on the non-precious metal Ni-based catalyst through the modulation effect of adding additives. It is used to directly oxidize methane to produce synthesis gas under the condition of large space velocity, and its activity is close to that of the noble metal catalyst under the same condition.
本发明的催化剂中主活性组分为Ni，担载在热稳定性好的α-Al2O3上，其特征在于添加助剂稀土和碱土金属元素进行调变作用，活性组分和助剂是以氧化物担载在载体上。催化剂组成的重量百分比是Ni:5～12％，稀土和碱土金属分别为1.5～5％和0.5～2％，其余部分为α-Al2O3。上述稀土可以是La、Ce或Pr中一种或几种混合物。In the catalyst of the present invention, the main active component is Ni, which is carried on α-Al 2 O 3 with good thermal stability, and is characterized in that additives such as rare earth and alkaline earth metal elements are added for modulation, and the active components and additives It is carried on the carrier by oxide. The weight percent of the catalyst composition is Ni: 5-12%, rare earth and alkaline earth metal 1.5-5% and 0.5-2% respectively, and the rest is α-Al 2 O 3 . The above-mentioned rare earths may be one or a mixture of La, Ce or Pr.
本发明的催化剂制备过程是采用Ni、稀土和碱土金属的硝酸盐溶液用分步浸渍法，将活性组分和助剂组分担载在担体上。经干燥后于750～900℃下进行焙烧2～10小时制得成品。上述浸渍顺序为用碱土、稀土、Ni硝酸盐进行。The preparation process of the catalyst of the invention adopts the nitrate solution of Ni, rare earth and alkaline earth metal to adopt step-by-step impregnation method, and loads the active component and the auxiliary component on the carrier. After drying, it is baked at 750-900°C for 2-10 hours to obtain a finished product. The above impregnation sequence is carried out with alkaline earth, rare earth, Ni nitrate.
本发明的催化剂用于甲烷直接氧化制合成气，其操作条件为：空速：1～7×105h-1,CH4/O2=1.75～2.3，反应温度：600～1000℃。The catalyst of the invention is used to directly oxidize methane to produce synthesis gas, and its operating conditions are: space velocity: 1-7×10 5 h -1 , CH 4 /O 2 =1.75-2.3, and reaction temperature: 600-1000°C.
下面通过实施例和比较例对本发明的技术给予进行一步说明。The technology of the present invention is described further below by way of examples and comparative examples.
实施例1催化剂的制备1The preparation of embodiment 1 catalyst 1
称取0.191克Ca(NO3)2·4H2O,0.136克La(NO3)3·4H2O,1.245克Ni(NO3)2·6H2O，各自溶解在适量去离子水中配成溶液，用3克α-Al2O3(30目～40目)分步依次浸渍上述溶液各18小时，浸渍样在50～60℃蒸干，在110～120℃烘8小时，然后在800℃空气中焙烧6小时。Weigh 0.191 g of Ca(NO 3 ) 2 ·4H 2 O, 0.136 g of La(NO 3 ) 3 ·4H 2 O, and 1.245 g of Ni(NO 3 ) 2 ·6H 2 O, and dissolve them in appropriate amount of deionized water to prepare solution, with 3 grams of α-Al 2 O 3 (30 mesh ~ 40 mesh) to impregnate the above solution step by step for 18 hours each, the impregnated sample was evaporated to dryness at 50 ~ 60 ° C, baked at 110 ~ 120 ° C for 8 hours, and then dried at 800 °C in air for 6 hours.
实施例2催化剂的制备2The preparation of embodiment 2 catalyst 2
称取0.316克Mg(NO3)2·6H2O,0.156克Ce(NO3)3·4H2O,1.314克Ni(NO3)2·6H2O，各自溶解在适量去离子水中配成溶液，用3克α-Al2O3(30目～40目)分步依次浸渍上述溶液各18小时，浸渍后的处理条件同例1。Weigh 0.316 g of Mg(NO 3 ) 2 ·6H 2 O, 0.156 g of Ce(NO 3 ) 3 ·4H 2 O, and 1.314 g of Ni(NO 3 ) 2 ·6H 2 O, and dissolve them in appropriate amount of deionized water to prepare Solution, with 3 grams of α-Al 2 O 3 (30 mesh to 40 mesh) to impregnate the above solutions step by step and sequentially for 18 hours. The treatment conditions after immersion are the same as in Example 1.
实施例3催化剂的性能1Performance 1 of embodiment 3 catalyst
催化剂活性的测定：采用固定床流动反应装置，利用实例1的催化剂，取催化剂0.03ml(40mg颗粒为30～40目)装于直径为4mm的石英反应管中。原料气CH4和O2(CH4/O2=2.0，摩尔比)进入反应管，流速为250ml/min。测温热偶插入催化剂床层中以测定床层温度。产物用气相色谱仪检测。The measurement of catalyst activity: adopt fixed-bed flow reaction device, utilize the catalyst of example 1, take catalyst 0.03ml (40mg particle is 30～40 meshes) and be packed in the quartz reaction tube that diameter is 4mm. Feed gas CH 4 and O 2 (CH 4 /O 2 =2.0, molar ratio) enter the reaction tube at a flow rate of 250ml/min. A thermocouple was inserted into the catalyst bed to measure the bed temperature. The product was detected by gas chromatography.
表1 Ni-La-Ca/α-Al2O3催化剂性能的考察Table 1 Investigation of Ni-La-Ca/α-Al 2 O 3 catalyst performance
催化剂 甲烷转化率 CO选择性 H2选择性H2/CO床层温度(℃) (％) (％) (％) 比率720 81.7 87.8 95.0 2.16760 85.3 90.2 96.4 2.14800 88.4 92.7 97.2 2.10840 91.3 94.7 98.0 2.07900 94.4 96.5 98.9 2.05Catalyst Methane conversion CO selectivity H 2 selectivity H 2 /CO bed temperature (°C) (%) (%) (%) ratio 720 81.7 87.8 95.0 2.16760 85.3 90.2 96.4 2.14800 88.4 92.7 97.2 2.10840 91.3 94.7 9490 90.9 98.9 2.05
实施例4催化剂的性能2Performance 2 of embodiment 4 catalyst
利用实例1,2的催化剂及实例3的装置和条件，进行助剂对催化性能和抗积碳能力的影响试验，其结果和反应条件列于表2和表3Utilize the catalyzer of example 1,2 and the device and condition of example 3, carry out the impact test of auxiliary agent on catalytic performance and anti-coking ability, its result and reaction condition are listed in table 2 and table 3
实施例5催化剂的性能3Performance 3 of embodiment 5 catalyst
利用实例2的催化剂及实例3的装置和条件，进行催化剂斩稳定性考察，反应条件：空速=5×105h-1,CH4/O2=2.0，催化剂层温度：780℃。连续反应100小时，催化剂的活性不变(CH4转化率为87％),H2和CO的选择性及H2/CO比率也保持稳定(H2选择性96％,CO选择性94％,H2/CO为2)。Using the catalyst of Example 2 and the equipment and conditions of Example 3, the stability of the catalyst was investigated. The reaction conditions were: space velocity=5×10 5 h -1 , CH 4 /O 2 =2.0, catalyst layer temperature: 780°C. Continuous reaction for 100 hours, the activity of the catalyst remained unchanged (CH 4 conversion rate was 87%), the selectivity of H 2 and CO and the ratio of H 2 /CO also remained stable (H 2 selectivity 96%, CO selectivity 94%, H 2 /CO is 2).
比较例1催化剂的活性比较The activity comparison of comparative example 1 catalyst
按实例1～2的催化剂的制备方法，制得含Ni及稀土或碱土金属组分量相同的催化剂，并用实例3的装置和条件进行试验，其结果分别列入表2和表3。Press the preparation method of the catalyzer of example 1～2, make the catalyzer that contains Ni and rare earth or alkaline earth metal component amount identical, and test with the device of example 3 and condition, its result is listed in table 2 and table 3 respectively.
表2助剂对催化剂活性的影响催化剂 反应温度 甲烷转化率 CO选择性 H2选择性 H2/CO担体α-Al2O3(℃) (％) (％) (％)Ni 910 92.7 94.8 98.8 22.08Ni-Mg 890 94.1 96.2 99.3 2.07Ni-La 900 94.5 96.2 98.8 2.05Ni-Ce 890 93.8 95.6 98.9 2.07Ni-Ce-Mg 910 95.6 96.0 99.8 2.08Ni-La-Ca 900 94.4 96.5 98.9 2.05反应条件：空速：5×105h-1,CH4/O2=2.0。Table 2 Effect of additives on catalyst activity Catalyst Reaction temperature Methane conversion CO selectivity H 2 selectivity H 2 /CO support α-Al 2 O 3 (°C) (%) (%) (%)Ni 910 92.7 94.8 98.8 22.08ni-Mg 890 86.2 99.3 2.07NI-LA 900 94.5 96.2 98.8 2.05NI-CE 890 93.8 95.9 2.07NI-CE-MG 95.6 96.0 99.8 2.08NI-CA 94.4 96.5 98.9 2.05 Holder: : 5×10 5 h -1 , CH 4 /O 2 =2.0.
表3不同催化剂上抗积碳性能的考察催化剂 Ni Rh Ni-La Ni-Ce Ni-Mg Ni-La-Ca Ni-Ce-Mg载体α-Al2O3积碳量 6.37 0.4 6.76 5.92 4.69 2.10 1.0Table 3 Investigation of anti-coking properties on different catalysts Catalyst Ni Rh Ni-La Ni-Ce Ni-Mg Ni-La-Ca Ni-Ce-Mg Carrier α-Al 2 O 3 Carbon deposition 6.37 0.4 6.76 5.92 4.69 2.10 1.0
反应条件：空速：5×105h-1,CH4/O2=2.10反应时间：1.5小时。Reaction conditions: Space velocity: 5×10 5 h -1 , CH 4 /O 2 =2.10 Reaction time: 1.5 hours.
由上述实例和比较例的结果表示，本发明的催化剂用于甲烷直接氧化制合成气，该催化剂在大空速条件下，具有高活性，高选择性和抗积碳性能等优点。同时该催化剂制备过程简单，成本低廉，适于工业化生产中应用。The results of the above examples and comparative examples show that the catalyst of the present invention is used for the direct oxidation of methane to synthesis gas, and the catalyst has the advantages of high activity, high selectivity and anti-coking performance under high space velocity conditions. At the same time, the preparation process of the catalyst is simple, the cost is low, and the catalyst is suitable for application in industrial production.
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| CN96115030A CN1061320C (en) | 1996-01-17 | 1996-01-17 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
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| CN96115030A CN1061320C (en) | 1996-01-17 | 1996-01-17 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
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| CN1154944A CN1154944A (en) | 1997-07-23 |
| CN1061320C true CN1061320C (en) | 2001-01-31 |
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| CN1093433C (en) * | 1999-02-10 | 2002-10-30 | 石油大学(北京) | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process |
| CN103752315B (en) * | 2014-01-15 | 2016-08-10 | 易高环保能源研究院有限公司 | A metal-phase carrier-supported catalyst and its preparation method and application |
| CN104084211B (en) * | 2014-07-10 | 2017-01-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
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